The oxidation of alcohols with trichloroisocyanuric acid: pyridine from base to organocatalyst

Summeren, Ruben P. van; Romaniuk, Amy; Ijpeij, Edwin G.; Alsters, Paul L.

doi:10.1039/c2cy20403g

Cited by 12 publications

(5 citation statements)

References 6 publications

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“…Further a simple catalyst-1,3,5-trichloroisocyanuric acid (TCCA)-for promoting the condensation reactions of β-diketones or β-ketoesters and related amines during the preparation of compounds was accidentally discovered. Of note, TCCA has been previously reported as an inexpensive and relatively stable chlorination [32,33] and oxidation reagent [34,35] and our results therefore further expand the application scope of TCCA. However, some agents' relatively modest potency and pharmacokinetic properties remain drawbacks for future studies as optimal EZH2Is; for example, GSK-126 is only administered by injection due to its poor pharmacokinetic properties [30].…”

Section: Compoundsupporting

confidence: 73%

5-Hydroxyindole-Based EZH2 Inhibitors Assembled via TCCA-Catalyzed Condensation and Nenitzescu Reactions

Zhou

Sun

et al. 2020

Molecules

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5-Hydroxyindole derivatives have various demonstrated biological activities. Herein, we used 5-hydroxyindole as a synthetic starting point for structural alterations in a combinatorial process to synthesize 22 different compounds with EZH2 inhibitor pharmacophores. A series of 5-hydroxyindole-derived compounds were screened inhibitory activities against K562 cells. According to molecular modeling and in vitro biological activity assays, the preliminary structure-activity relationship was summarized. Compound L–04 improved both the H3K27Me3 reduction and antiproliferation parameters (IC50 = 52.6 μM). These findings revealed that compound L–04 is worthy of consideration as a lead compound to design more potent EZH2 inhibitors. During the preparation of compounds, we discovered that trichloroisocyanuric acid (TCCA) is a novel catalyst which demonstrates condensation-promoting effects. To gain insight into the reaction, in situ React IR technology was used to confirm the reactivity. Different amines were condensed in high yields with β-diketones or β-ketoesters in the presence of TCCA to afford the corresponding products in a short time (10~20 min), which displayed some advantages and provided an alternative condensation strategy.

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Section: Compoundsupporting

confidence: 73%

5-Hydroxyindole-Based EZH2 Inhibitors Assembled via TCCA-Catalyzed Condensation and Nenitzescu Reactions

Zhou

Sun

et al. 2020

Molecules

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“…For this, TCC is used both to activate and regenerate TEMPO in a two-step oxidation [ 26 ]. Since all three chlorine atoms are active, TCC can function three times as oxidation reagent and finally convert to cyanuric acid with an aromatic ring, which is the driving force for the reaction [ 31 ] ( Scheme 2 ). Additionally, the reaction must be performed under strictly anhydrous conditions to avoid subsequent oxidation to carboxylic acid functions [ 26 ].…”

Section: Discussionmentioning

confidence: 99%

TEMPO/TCC as a Chemo Selective Alternative for the Oxidation of Hyaluronic Acid

et al. 2021

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Hyaluronic acid (HA)-based hydrogels are very commonly applied as cell carriers for different approaches in regenerative medicine. HA itself is a well-studied biomolecule that originates from the physiological extracellular matrix (ECM) of mammalians and, due to its acidic polysaccharide structure, offers many different possibilities for suitable chemical modifications which are necessary to control, for example, network formation. Most of these chemical modifications are performed using the free acid function of the polymer and, additionally, lead to an undesirable breakdown of the biopolymer’s backbone. An alternative modification of the vicinal diol of the glucuronic acid is oxidation with sodium periodate to generate dialdehydes via a ring opening mechanism that can subsequently be further modified or crosslinked via Schiff base chemistry. Since this oxidation causes a structural destruction of the polysaccharide backbone, it was our intention to study a novel synthesis protocol frequently applied to selectively oxidize the C6 hydroxyl group of saccharides. On the basis of this TEMPO/TCC oxidation, we studied an alternative hydrogel platform based on oxidized HA crosslinked using adipic acid dihydrazide as the crosslinker.

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“…In our ongoing investigations on oxidation chemistry with 2‐iodoxybenzoic acid (IBX) and oxone,8 our attention was drawn toward trichloroisocyanuric acid (TCCA), which has been reported to be a versatile and innocuous oxidant with high stability 9a–9c. In the realm of synthetic organic chemistry, TCCA has been employed – due to its low price and ready availability, environmentally benign attributes, and ability to serve as a source of three chlorine atoms – for a variety of reactions that include oxidation of primary and secondary alcohols to their corresponding aldehydes and ketones,10a conversion of alcohols into alkyl chlorides,10b preparation of alkyl halides from alcohols,10c dihalogenation of olefins,10d halogenation of 1,3‐dicarbonyl compounds,10e halofluorination of alkenes,10f aromatic halogenations,10g and N ‐halogenation 9b–9d.…”

Section: Introductionmentioning

confidence: 99%

Trihaloisocyanuric Acids as Atom‐Economic Reagents for Halogenation of Aromatics and Carbonyl Compounds in the Solid State by Ball Milling

2015

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It is shown that both tribromoisocyanuric acid (TBCA) and trichloroisocyanuric acid (TCCA) are excellent reagents for direct halogenation of electron‐rich aromatics under solvent‐free, ball‐milling conditions. The results are remarkable in light of the fact that chlorination of aromatics without any acid catalyst is heretofore unknown. The procedure is operationally simple, and the reactions occur within a few hours, affording high yields of halogenated products. Similarly, crystalline β‐keto dicarbonyl compounds are shown to undergo direct α,α‐dihalogenation with TBCA and TCCA with ball milling. Whereas monoketones are found to be unreactive with TBCA/TCCA, addition of 25 mol‐% of p‐toluenesulfonic acid as a solid catalyst catalyzes the reaction, leading to the formation of α‐chloro/bromo ketones in very good isolated yields. The fact that each of the reagents, in principle, serves as a source of three halogen atoms should render solvent‐free halogenation of aromatics and carbonyl compounds with TBCA/TCCA an invaluable synthetic protocol.

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The oxidation of alcohols with trichloroisocyanuric acid: pyridine from base to organocatalyst

Cited by 12 publications

References 6 publications

5-Hydroxyindole-Based EZH2 Inhibitors Assembled via TCCA-Catalyzed Condensation and Nenitzescu Reactions

5-Hydroxyindole-Based EZH2 Inhibitors Assembled via TCCA-Catalyzed Condensation and Nenitzescu Reactions

TEMPO/TCC as a Chemo Selective Alternative for the Oxidation of Hyaluronic Acid

Trihaloisocyanuric Acids as Atom‐Economic Reagents for Halogenation of Aromatics and Carbonyl Compounds in the Solid State by Ball Milling

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